EP1029879B1 - Aquous dispersion containing a surface-deactivated polyisocyanate - Google Patents
Aquous dispersion containing a surface-deactivated polyisocyanate Download PDFInfo
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- EP1029879B1 EP1029879B1 EP00109963A EP00109963A EP1029879B1 EP 1029879 B1 EP1029879 B1 EP 1029879B1 EP 00109963 A EP00109963 A EP 00109963A EP 00109963 A EP00109963 A EP 00109963A EP 1029879 B1 EP1029879 B1 EP 1029879B1
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- Prior art keywords
- polyisocyanate
- reactive
- polymer
- temperature
- adhesive
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
- C08G18/8058—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38 with compounds of C08G18/3819
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
Definitions
- the invention relates aqueous dispersions, the surface deactivated polyisocyanates and isocyanate reactive polymers contain.
- JP 09 188,735 describes a mixture of dispersed which is stable in storage at room temperature functional polymers with a polyisocyanate.
- a predispersion consisting of Polyisocyanate, polymeric stabilizer and a hydrophobic liquid (as a dispersing agent) is in a further aqueous solution or dispersion of an isocyanate-reactive Polymers emulsified with the help of an o / w emulsifier and protective colloid. After The application and evaporation of the water spontaneously reacts under Crosslinking with the functional groups of the polymer.
- DE 31 12 054 DE 32 28 723 and DE 32 28 724 powdery, finely divided solid Polyisocyanates with particle diameters up to 150 ⁇ m surface deactivated. Due to the surface coating, the polyisocyanates retain their isocyanate content and their reactivity and form a stable one-component system even in water or aqueous solvents.
- a method for producing stable dispersions of finely divided surface deactivated Isocyanates are described in DE 35 17 333.
- the resulting stable dispersions are suitable as crosslinking agents.
- WO 93/25599 Storage-stable, latent-reactive masses or layers are described in WO 93/25599. These consist of isocyanate-functional polymers that have a melting point above 40 ° C have and surface deactivated polyisocyanates. For the preparation of the mixture the components are melted to temperatures that are significantly higher than the Softening point of the polymer. The equipment expenditure for the production and the application of these masses are considerable in addition to the energy costs. In addition, in only systems deactivated for stability and processing reasons Polyisocyanates are used that have a crosslinking temperature of over 80 ° C exhibit. Furthermore, a targeted and controlled inhomogeneous mixing of the Components subject of registration. However, this requires complex Operations.
- the object of the present invention is storage-stable, latent-reactive, largely dry Produce layers or powders, including deactivated polyisocyanates with reaction temperatures below 80 ° C can be used, which are from an environmental point of view behave advantageously and can also be produced inexpensively.
- Storage stable, latent reactive layers or powders can be produced by the use of a substantially aqueous dispersion which is at least one surface-deactivated polyisocyanate and at least one dispersed or dissolved with Contains isocyanate reactive polymer.
- the result is an anhydrous, dry, latent-reactive film or a latent-reactive film Powder that can be stored at room temperature or at a slightly elevated temperature.
- the Reactivity of the surface deactivated isocyanates with the functional groups of the polymer is obtained.
- a molten system results after the water has evaporated.
- An example is the gluing of a laminate made of foils. They are also in this phase surface deactivated isocyanates unchanged and retain their reactivity.
- the Bonding is initially based on the thermoplastic properties of the polymer.
- reaction or thickening temperatures of the deactivated Polyisocyanates should have temperatures in the range from 30 ° C to 180 ° C, are preferably in the range between 40 ° C and 150 ° C.
- Thickening or reaction temperature refers to the temperature at which the surface-deactivating layer of the isocyanate dissolves in the polymer or in another way gets destroyed. The polyisocyanate is released and dissolved in the polymer. The final curing takes place by diffusion and reaction of the polyisocyanate with the functional groups of the Polymers with increased viscosity and crosslinking. The thickening and Depending on the type of surface-deactivated polyisocyanate, the reaction temperature is higher or lower below the softening temperature of the polymer.
- the stability of the unreacted system, the reaction temperature and the course of the reaction are determined by the type of polyisocyanate, the type and amount of surface stabilizer, by the solubility parameter of the functional polymer and by catalysts, Plasticizers and other auxiliaries. These are largely in the beginning property rights mentioned.
- the application is followed by processing steps of the layer or the Powder-bearing substrate subject of the invention.
- steps as e.g. when processing the substrate into its final shape by punching, cutting, Bending, folding, laminating, etc. are necessary.
- the layer or powder can are heated to temperatures above the softening temperature of the polymer without that reaction between the functional groups of the polymer and the surface deactivated isocyanates occurs. Processing in the plastic state can take place even with repeated heating and cooling.
- the films or powders are preferably storage-stable, latent-reactive Adhesive systems.
- All di- or polyisocyanates are suitable as polyisocyanates for the process or mixtures thereof, provided that they have a melting point above 40 ° C. and convert into powder form with particle sizes below 200 ⁇ m by known methods to let. It can be aliphatic, cycloaliphatic, heterocyclic or aromatic Be polyisocyanates.
- Examples include: diphenylmethane-4,4'-diisocyanate (MDI), Naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-biphenyl-4,4'-diisocyanate (TODI), dimeric 1-methyl-2,4-phenylene diisocyanate (TDI-U), 3,3'-diisocyanato-4,4'-dimethyl-N, N'diphenylurea (TDIH), addition product of 2 moles of 1-methyl-2,4-phenylene diisocyanate with 1 mol of 1,2-ethanediol, 1,4-butanediol, 1,4-cyclohexane-di-methanol, or ethanolamine, the Isocyanurate from IPDI (IPDI-T).
- MDI diphenylmethane-4,4'-diisocyanate
- NDI Naphthalene-1,5-diiso
- Addition products from 1-methyl-2,4-phenylene diisocyanate and 1,4 butanediol or 1,2 ethanediol are also available in solid and liquid solvents or solvent-free systems very advantageous properties. These show up all with regard to their low curing or crosslinking temperature, which in Temperature range is below 90 ° C. So the use of this mixture is now largely water or polyol based very beneficial for coatings and Bonding of temperature sensitive substrates.
- the concentration of the deactivating agent should be 0.1 to 25, preferably 0.5 to 8 equivalent percent amount, based on the total isocyanate groups present.
- the particle size of the powdery powder must often be used Polyisocyanates, by a fine dispersion downstream of the synthesis or Wet grinding can be brought to a particle size in the range of 0.5 to 20 microns. Therefor dissolvers, rotor-stator type dispersers, agitator ball mills, Perlund are suitable Sand mills, ball mills and attrition mills, at temperatures below 40 ° C.
- dissolvers rotor-stator type dispersers, agitator ball mills, Perlund are suitable Sand mills, ball mills and attrition mills, at temperatures below 40 ° C.
- the ground and surface stabilized polyisocyanate can also be separated from the grinding dispersions and dried.
- catalysts can also be added.
- Preferred catalysts are those which are stable to hydrolysis in aqueous solution or dispersion and then later also accelerate the heat-activated reaction.
- urethane catalysts are organic tin, iron, lead, cobalt, bismuth, antimony, zinc compounds or their mixtures. Alkyl mercaptide compounds of dibutyltin are preferred due to their higher hydrolysis stability.
- Tertiary amines such as dimethylbenzylamine, diazabicyclo-undecene, and non-volatile polyurethane foam catalysts based on tertiary amine can be used for special purposes or in combination with metal catalysts, but the Catalan activity can be impaired by reaction with the carbon dioxide in the air.
- the concentration of the catalysts is in the range from 0.001 to 3%, preferably 0.01%. 1% based on the reactive system.
- reaction partner of the polyisocyanates according to the invention become polyurethanes with primary and secondary amino groups or partially saponified polyvinyl acetate used.
- This reaction increases the reactivity of the functional groups of the polymer the isocyanate groups, at the expense of the side reaction with water.
- water-soluble hydroxyl-functional binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, hydroxyethyl cellulose, hydroxypropyl cellulose, and water-dispersible hydroxyl-functional polyesters, hydroxyl-functional sulfopolyesters, and polyurethane dispersions, dispersions of polyamidoamines which carry carboxyl, hydroxyl primary or secondary amino groups.
- aqueous colloidal dispersions or colloidal solutions with particle sizes between 1 - 100 nm can be produced in colloid mills, starting from thermoplastic polymers with isocyanate-reactive groups. Examples are high molecular weight solid epoxy resins, poly-ethylene-vinyl alcohol and poly-ethylene-co-acrylic acid.
- the ratio between the isocyanate groups in the surface-stabilized fine particles Polyisocyanates and the sum of the hydroxyl and amino groups of the polymers in the largely anhydrous and solid state should be in the range 0.1 to 1.5.
- inert substances can be added to the resulting high-viscosity paste or low-viscosity mixture or functional additives can be mixed or dispersed.
- functional Additives include hydroxy or amino functional powdered or liquid low to high molecular compounds, which with the solid polyisocyanates above the Reaction temperature can react. The stoichiometric ratios are corresponding adapt.
- low molecular weight compounds are compounds with Molecular weights between 40 and 500 g / mol understood by high molecular weight Compounds those whose molecular weights are between 500 and 10,000 g / mol.
- low molecular weight to high molecular weight liquid polyols or / and polyamines solid polyfunctional polyols and / or aromatic polyamines.
- examples are triethanolamine, butanediol, trimethylolpropane, ethoxylated bisphenol A, terminally ethoxylated polypropylene glycols, 3,5-diethyl-toluylene-2,4- and 2-6-diamine, Poly-tetramethylene oxide di (p-aminobenzoate), tris-hydroxyethyl isocyanurate, hydroquinone bis-hydroxyethyl ether, Pentaerythritol, 4,4'-diamino-benzanilide, 4,4'-methylene-bis- (2,6-diethylaniline).
- the inert additives include, for example, wetting agents, organic or inorganic Thickeners, plasticizers, fillers, plastic powders, pigments, dyes, Light stabilizers, aging stabilizers, corrosion inhibitors, flame retardants, Blowing agents, adhesive resins, organofunctional silanes, short cut fibers and optionally small amounts of inert solvents.
- the advantages of the present invention lie in the separation of application of the aqueous dispersion from the crosslinking reaction i.e. the final curing.
- adhesive films on wood, glass or other substrates or Document are applied, these prefabricated products are stored and / or sent and be cured to the final product in another location.
- Another advantage of the method and the use of the corresponding Products lie in the use of water as the dispersion medium Energy consumption for the production of the dispersions is low.
- the proportion of organic Solvent minimal, which in a very environmental sense advantageous processing results.
- the cross-linking temperatures can range from 35 ° C to 90 ° C. With these low Cross-linking temperatures can also be used with temperature-sensitive substrates One-component system can be glued by heat.
- the layer or powder obtained from the aqueous suspension, dispersion or solution can be stored for months.
- the storage period at room temperature or slightly elevated temperatures however different.
- the storage period of the system according to the invention in anhydrous and uncrosslinked state is at least 3 times, usually more than 10 times same mixture with the same polyisocyanates, which is not surface-deactivated are.
- the layers or powders according to the invention are at least six months stable in storage, but at least 1 month stable at room temperature and according to the invention processable.
- latent-reactive essentially describes the state of the anhydrous layer or powder in which the surface deactivated polyisocyanate and the polymer which is reactive with isocyanates is present in a substantially uncrosslinked state.
- the heat supply for thermoplastic processing and crosslinking can preferably with convection or radiant heat.
- the storage-stable watery Suspension, dispersion or solution of surface deactivated fine particles Polyisocyanates and dispersed or water-soluble polymers with isocyanate-reactive Groups can be on the surface of the substrate to be glued or coated are applied, in particular by brushing, spraying, spraying, knife coating, filling, Casting, dipping, extruding or applied by roller application or in the printing process become.
- the storage-stable aqueous dispersion of surface deactivated fine particle polyisocyanates and dispersed or Water-soluble polymers with isocyanate-reactive groups can take the form of a latent-reactive Adhesive film, adhesive tape, adhesive fleece or tissue are brought, the two-sided adhesion can build up.
- the dispersion according to the invention applied to a non-adhesive carrier tape or release paper and the water at room temperature or at temperatures up to the softening temperature of the polymer evaporates. After cooling, the adhesive film can be detached from the carrier and be stored carrier-free until use. Alternatively, the adhesive film can be used the backing paper are stored together.
- the reactive dispersion is sprayed, Spraying, knife coating, pouring, dipping, padding, by roller application or in Applied printing process, the water at room temperature or at temperatures up to Softening temperature of the polymer evaporates, and the adhesive fleece or fabric, provided or impregnated with the latently heat-reactive adhesive layer until use stored.
- the carrier-free adhesive films, tapes, adhesive fleeces or fabrics serve as an adhesive layer between substrates. It is also possible to apply adhesive films, fleeces or fabrics on one side Apply or sinter the substrate surface in the plastic state. This laminate can be up to for final gluing with a second substrate surface at room temperature be stored.
- the storage-stable aqueous dispersion of surface deactivated fine particle polyisocyanates and dispersed or Water-soluble polymers with isocyanate-reactive groups can take the form of a latent-reactive Powder are brought. These powders can be used as latent reactive adhesives or for coating purposes, like powder coatings.
- these can be in be sprayed into a spray tower.
- the temperature of the air introduced from below should below the softening temperature of the polymer and the reaction temperature of the surface-blocked polyisocyanate remain.
- the dispersions according to the invention can be applied to the non-stick surface of a circumferential tape sprayed with adhesive surfaces or with a Printing processes can be applied. After the water has evaporated, the dry particles scraped off the belt, sieved and classified if necessary, and up to Use stored.
- Latent reactive powders can also be made from unsupported films or tapes Milling processes, possibly at low temperatures, are produced. They serve as heat-reactive crosslinkable adhesive or as a coating powder. Application devices and Methods are known in the art and known to the person skilled in the art.
- the latent reactive prefabricated manufactured with the method Layers preferably serve as a thermally resilient adhesive connection for flexible or solid substrates such as Metals, plastics, glass, wood, wood composites, cardboard, Foils, synthetic fabrics, textiles ,.
- the reactive coating powders thus produced can also be used with the Process application methods for powder coatings.
- the crosslinking temperature can vary Selection of the polyisocyanate should be so low that heat-sensitive substrates, such as plastics, Textiles and wood can be coated without thermal damage.
- the process also only allows the coating powders on the substrate to be sintered or sintered to melt a closed layer. The complete networking then takes place at one later heat treatment, possibly after an additional mechanical or thermal processing step.
- test specimens with 100x20x5 mm 3 made of beech wood resp. 25x100xd mm 3 made of synthetic material were simply overlapped press-glued, overlap 10 mm, adhesive surface 20x10 mm 2 .
- the wood specimens were heated in a forced air oven under vacuum (residual pressure 0.1 bar) at 120 ° C for 0.5 hours.
- test specimens were used to determine the temperature resistance after storage A to C. hung vertically in the convection oven and loaded with 300 g. The temperature became every 15
- Example 3 (1) (2) (3), components as above (4) polyamidoamine Euretek 505 144 3.7 5.0 (5) 3,3'-dimethyl-biphenyl-4,4'-di-isocyanate (TODI) 132 80
- Example 4 (1) (2) (3), components as above (4) polyamidoamine Euretek 505, or Jeffamin 403 144 3.3 5.0 (5) Dimeric 1-methyl-2,4-phenylene diisocyanate (TDI-U) 174 80
- Example 5 (1) (2) (3), components as above (4) polyamidoamine Euretek 505, 144 3.3 5.8 (5) urethane of 2 moles of 1-methyl-2,4-phenylene and 1 mole of 1,2-ethylene glycol (TDIxEG) 205 80
- Example 6 (1) (2) (3), components as above (4) polyamidoamine Euretek 505, 144 3.3 6.3 (5) urethane of 2 moles of 1-methyl-2,4-phenylene and 1 mole of 1,4-butanedi
- Adhesive dispersions used Jagotex KEM 2010 Vinyl acetate (meth) acrylate dispersion, with hydroxyl groups in the polymer and in the protective colloid, 55% solids, contact adhesive with activation temperature 60 - 80 ° C. Neutralized with ammonia.
- a reactive dispersion adhesive with the specified polyisocvanates was produced using the dissolver as follows: parts by weight parts by weight (1) Adhesive dispersion, approx. 50% solids 100 per 100 polymer (2) Suspension of deactivated polyisocyanate, approx. 35% 16 11.2 (3) Metatin catalyst 715; Based on dibutyltin alkyl mercaptide (Acima AG, CH-Buchs), 1 about 0.2 10% in diethylene glycol dimethyl ether 117
- the adhesive mixtures were applied to the adhesive surfaces of beech wood specimens with a spiral doctor blade, then treated in accordance with the bearings A - C, then tested as indicated.
- the application weight after drying was about 100 g / m 2 .
- Example 12 Dispersion adhesive with SDSI suspension (note 1) Without SDSI Desmodur DA (note 2) IPDI-T Susp. according to example 1 MDI Susp. according to example 2 TODI Susp. according to example 3 Storage A: 30 min.
- Example 16 Dispersion adhesive with SDSI suspension (note 1) TDI-U Susp. according to example 4 TDIxEG Susp. according to example 5 TDIxEG Susp. according to Example 5 One-sided order TDIxBDO Susp. according to example 6 Storage A: 30 min.
- Example 21 Dispersion adhesive with SDSI suspension (note 1) Without SDSI Desmodur DA (note 2) IPDI-T Susp. according to example 1 TDI-U Susp. according to example 4 TDIxEG Susp. according to example 5 Storage A: 30 min.
- thermoreactive adhesive fleece
- the adhesive dispersions were applied with a spiral doctor blade to spunbonded fabrics made of polyethylene terephthalate (Lutradur 7225, basis weight 25 g / m2, Freudenberg KG, D-Weinheim).
- the Nonwovens were separated from the base in the fresh state and hung vertically Normal conditions dried.
- Example 22 Example 23
- Example 24 Adhesive according to the example 13 13 16 with polymer KEM 2010 KEM 2010 KEM 2010 SDSI short name TDI-U TDI-U TDIxBDO Application weight, dry; g / m2 88 25 34 Heat resistance of the adhesive joints ° C > 150 > 150 > 150
- Example 22 was repeated analogously, spunbonded fabrics being dispensed with. It came into being a completely carrier-free, firm adhesive layer, which when tested for heat resistance the Example 22 showed analog values.
- the reactive adhesive dispersion according to Example 14 was applied to test specimens with the dimensions 100 ⁇ 25 ⁇ 3 mm 3 , dry weight approx. 100 g / m 2 . After the water had evaporated, the test specimens were stored for 3 days under normal conditions. The coated surfaces were heated to 80 ° C. (i.e. just above the softening point of the polymer) and a simply overlapping press bond, adhesive surface 200 mm 2 , was produced. The temperature was immediately raised to 120 ° C. and held for 30 minutes. The crosslinking takes place at this temperature. Then store for 24 hours under normal conditions. The following were determined: Tensile shear strength (100 mm per minute tensile speed) 2.21 MPa Heat resistance > 150 ° C
- Example 13 An adhesive composition was prepared analogously to Example 13 and the aqueous one Dispersion applied at room temperature. The water was removed by Evaporation at room temperature and / or penetration into the mat. The solid layer was left open for a period of 5 months at + 2 ° C. The adhesive surfaces were then assembled and clamped at 120 ° C for 0.5 hours heated, whereby the crosslinking reaction was triggered. Finally there was a 24th hours storage at room temperature at room temperature. The results regarding Heat resistance and water storage corresponded to those in Example 13.
- Example 13 Production, application and storage were carried out analogously to Example 26. After that it was finished Underlay and solid adhesive layer existing system three times to 80 ° C above the Softening point of the polymer warmed and cooled again. Then it happened Cure by heating to 120 ° C for half an hour. The results regarding Heat resistance and water storage corresponded to those in Example 13.
- Example 13 An aqueous dispersion which corresponded to the composition from Example 13 was removed using Spray drying converted into a solid, largely anhydrous powder.
- the application, Storage and crosslinking were carried out in the same way as storage C. Heat resistance and water storage corresponded to those in Example 13.
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft wässrige Dispersionen, die oberflächendesaktivierte Polyisocyanate und isocyanatreaktive Polymere enthalten.The invention relates aqueous dispersions, the surface deactivated polyisocyanates and isocyanate reactive polymers contain.
JP 09 188,735 beschreibt ein bei Raumtemperatur lagerstabiles Gemisch aus dispergierten funktionellen Polymeren mit einem Polyisocyanat. Eine Vordispersion bestehend aus Polyisocyanat, polymerem Stabilisator und einer hydrophoben Flüssigkeit (als Dispersionsmittel) wird in einer weiteren wässerigen Lösung oder Dispersion eines isocyanatreaktiven Polymeren unter Zuhilfenahme eines o/w Emulgators und Schutzkolloids emulgiert. Nach der Applikation und dem Verdunsten des Wassers reagiert das Polyisocyanat spontan unter Vernetzung mit den funktionellen Gruppen des Polymeren.JP 09 188,735 describes a mixture of dispersed which is stable in storage at room temperature functional polymers with a polyisocyanate. A predispersion consisting of Polyisocyanate, polymeric stabilizer and a hydrophobic liquid (as a dispersing agent) is in a further aqueous solution or dispersion of an isocyanate-reactive Polymers emulsified with the help of an o / w emulsifier and protective colloid. After The application and evaporation of the water spontaneously reacts under Crosslinking with the functional groups of the polymer.
In DE 31 12 054, DE 32 28 723 und DE 32 28 724 werden pulverförmige, feinteilige feste Polyisocyanate mit Teilchendurchmessern bis 150 µm oberflächlich desaktiviert. Durch die Oberflächenbeschichtung behalten die Polyisocyanate ihren Isocyanatgehalt und ihre Reaktivität und bilden ein stabiles Einkomponentensystem auch in Wasser oder wässerigen Lösungsmitteln.In DE 31 12 054, DE 32 28 723 and DE 32 28 724 powdery, finely divided solid Polyisocyanates with particle diameters up to 150 µm surface deactivated. Due to the surface coating, the polyisocyanates retain their isocyanate content and their reactivity and form a stable one-component system even in water or aqueous solvents.
Im DE 32 28 724 und DE 32 30 757 werden oberflächendesaktivierte pulverförmige Diisocyanate mit Polyolen und wässerigen Dispersionspolymeren, die funktionelle Gruppen enthalten zu einer lagerstabilen reaktiven Paste kombiniert. Durch Aufheizen dieser wasserhaltigen Paste auf 140°C, d.h. über die Reaktionstemperatur des Polyisocyanates vernetzen diese beiden Komponenten und es wird ein leicht angeschäumter elastischer Belag erhalten.In DE 32 28 724 and DE 32 30 757 surface deactivated powder are Diisocyanates with polyols and aqueous dispersion polymers, the functional groups contain combined to a storage stable reactive paste. By heating this up water-containing paste at 140 ° C, i.e. about the reaction temperature of the polyisocyanate network these two components and it becomes a slightly foamed elastic covering receive.
Ein Verfahren zur Herstellung stabiler Dispersionen feinteiliger oberflächendesaktivierten Isocyanate wird in DE 35 17 333 beschrieben. Die resultierenden stabilen Dispersionen eignen sich als Vernetzungsmittel.A method for producing stable dispersions of finely divided surface deactivated Isocyanates are described in DE 35 17 333. The resulting stable dispersions are suitable as crosslinking agents.
Eine Verwendung der wässerigen Dispersionen von oberflächendesaktivierten festen, feinteiligen Polyisocyanaten als Vernetzer in Textilpigmentdruckpasten und Färbeflotten wird in DE 35 29 530 dargelegt. Im Anschluss an den Applikationsvorgang werden die Textilpigmentdruckpasten und Färbeflotten mit Heissluft oder Dampf auf dem Gewebe fixiert.Use of the aqueous dispersions of surface deactivated solid, finely divided polyisocyanates as crosslinkers in textile pigment printing pastes and dyeing liquors set out in DE 35 29 530. Following the application process, the textile pigment printing pastes and dye liquors fixed on the fabric with hot air or steam.
Nachteil dieser in diesen Dokumenten beschriebenen Systeme ist jedoch, dass die Arbeitsschritte Applikation und Aushärten bzw. Vernetzen nicht getrennt werden können, was sowohl aus ökonomischen wie logistischen Gründen bei einer Vielzahl von Anwendungen wünschenswert erscheint. However, the disadvantage of the systems described in these documents is that the Work steps application and curing or cross-linking cannot be separated, for both economic and logistical reasons with a large number of Applications seems desirable.
So würde ein Substrat, das eine lagerstabile latent-reaktive Schicht oder Pulver trägt die Möglichkeit eröffnen, an dem Ort aufgetragen zu werden, an dem die entsprechenden Gerätschaften vorhanden sind, eine vorbestimmbare Zeitspanne gelagert zu werden und anschliessend zu dem Ort transportiert zu werden, an dem die Verarbeitung zu weiteren Zwischenprodukten oder zum Endprodukt erfolgt.So would a substrate that carries a storage-stable latent-reactive layer or powder Open the possibility to be applied in the place where the corresponding Equipment are available to be stored and a predetermined period of time then to be transported to the place where the processing for further Intermediates or the end product.
Lagerstabile, latent-reaktive Massen oder Schichten werden in WO 93/25599 beschrieben. Diese bestehen aus isocyanatfunktionellen Polymeren, die einen Schmelzpunkt über 40°C aufweisen und oberflächendesaktivierten Polyisocyanaten. Zur Herstellung des Gemisches werden die Komponenten auf Temperaturen aufgeschmolzen, die wesentlich über dem Erweichungspunkt des Polymeren liegen. Der apparative Aufwand für die Herstellung und die Applikation dieser Massen sind neben den Energiekosten erheblich. Zudem können in diesem Systemen aus Stabilitäts- und Verarbeitungsgründen nur oberflächendesaktivierte Polyisocyanate verwendet werden, die eine Vernetzungstemperatur von über 80 °C aufweisen. Weiterhin ist eine gezielte und kontrollierte inhomogene Vermischung der Komponenten Gegenstand der Anmeldung. Diese erfordert jedoch aufwendige Arbeitsschritte.Storage-stable, latent-reactive masses or layers are described in WO 93/25599. These consist of isocyanate-functional polymers that have a melting point above 40 ° C have and surface deactivated polyisocyanates. For the preparation of the mixture the components are melted to temperatures that are significantly higher than the Softening point of the polymer. The equipment expenditure for the production and the application of these masses are considerable in addition to the energy costs. In addition, in only systems deactivated for stability and processing reasons Polyisocyanates are used that have a crosslinking temperature of over 80 ° C exhibit. Furthermore, a targeted and controlled inhomogeneous mixing of the Components subject of registration. However, this requires complex Operations.
Aufgabe der vorliegenden Erfindung ist es lagerstabile, latent-reaktive, weitgehend trockene Schichten oder Pulver herzustellen, bei dem auch desaktivierte Polyisocyanate mit Reaktionstemperaturen unter 80°C einsetzbar sind, die sich unter Umweltschutzgesichtspunkten vorteilhaft verhalten und zusätzlich kostengünstig produziert werden können.The object of the present invention is storage-stable, latent-reactive, largely dry Produce layers or powders, including deactivated polyisocyanates with reaction temperatures below 80 ° C can be used, which are from an environmental point of view behave advantageously and can also be produced inexpensively.
Erfindungsgemäss wird dies durch durch die Kennzeichen der unabhängigen Ansprüche gelöst.According to the invention, this is achieved by the characteristics of the independent claims solved.
Lagerstabile, latent-reaktive Schichten oder Pulver können hergestellt werden durch die Verwendung einer im wesentlichen wässrigen Dispersion, die wenigstens ein oberflächendesaktiviertes Polyisocyanat und wenigstens ein dispergiertes oder gelöstes mit Isocyanat reaktives Polymer enthält.Storage stable, latent reactive layers or powders can be produced by the use of a substantially aqueous dispersion which is at least one surface-deactivated polyisocyanate and at least one dispersed or dissolved with Contains isocyanate reactive polymer.
Aus den erfindungsgemäßen Dispersionen lassen sich lagerstabile, latent-reaktive Schichten oder
Pulver herstellen indem eine Dispersion
gemäß Anspruch 1 dadurch bereitgestellt wird, dass
Überaschenderweise wurde gefunden, dass das Entfernen des Wassers und Trocknen des
Gemisches im Temperaturbereich wahlweise bei
Im Falle i) resultiert ein wasserfreier, trockener, latent-reaktiver Film oder ein latent-reaktives Pulver, welche bei Raumtemperatur oder bei leicht erhöhter Temperatur lagerfähig ist. Die Reaktionsfähigkeit der oberflächendesaktivierten Isocyanate mit den funktionellen Gruppen des Polymern wird erhalten.In case i) the result is an anhydrous, dry, latent-reactive film or a latent-reactive film Powder that can be stored at room temperature or at a slightly elevated temperature. The Reactivity of the surface deactivated isocyanates with the functional groups of the polymer is obtained.
Im Falle ii) resultiert nach dem Verdampfen des Wassers ein geschmolzenes System. Als Beispiel dient das Verkleben eines Laminates aus Folien. Auch in dieser Phase sind die oberflächendesaktivierten Isocyanate unverändert und behalten ihre Reaktivität. Die Verklebung basiert zunächst auf den thermoplastischen Eigenschaften des Polymers.In case ii), a molten system results after the water has evaporated. As An example is the gluing of a laminate made of foils. They are also in this phase surface deactivated isocyanates unchanged and retain their reactivity. The Bonding is initially based on the thermoplastic properties of the polymer.
In beiden Fällen vernetzt das System und es wird unschmelzbar und unlöslich erst bei Überschreiten der Reaktionstemperatur des oberflächendesaktivierten Isocyanats. Dies erfolgt nach einer vorbestimmbaren Zeitspanne.In both cases, the system networks and it becomes infusible and insoluble only at Exceeding the reaction temperature of the surface deactivated isocyanate. this happens after a predeterminable period of time.
In gewissen Fällen genügt ein kurzfristiges Überschreiten der Reaktionstemperatur, um die Vernetzungsreaktion auszulösen. Die Reaktions- oder Aufdicktemperaturen der desaktivierten Polyisocyanate sollten dabei Temperaturen im Bereich von 30°C bis 180°C aufweisen, bevorzugt im Bereich zwischen 40°C und 150°C liegen.In certain cases, a short-term exceeding of the reaction temperature is sufficient to achieve the Trigger crosslinking reaction. The reaction or thickening temperatures of the deactivated Polyisocyanates should have temperatures in the range from 30 ° C to 180 ° C, are preferably in the range between 40 ° C and 150 ° C.
Aufdickung- oder Reaktionstemperatur bezeichnet die Temperatur, bei der sich die oberflächendesaktivierende Schicht des Isocyanats im Polymer löst oder auf andere Weise zerstört wird. Das Polyisocyanat wird freigesetzt und im Polymer gelöst. Die Endaushärtung erfolgt durch Diffusion und Reaktion des Polyisocyanates mit den funktionellen Gruppen des Polymeren unter Viskositätsanstieg und Vernetzung. Die Aufdickungs- und Reaktionstemperatur liegt je nach Art des oberflächendesaktivierten Polyisocyanates oberoder unterhalb der Erweichungstemperatur des Polymeren. Thickening or reaction temperature refers to the temperature at which the surface-deactivating layer of the isocyanate dissolves in the polymer or in another way gets destroyed. The polyisocyanate is released and dissolved in the polymer. The final curing takes place by diffusion and reaction of the polyisocyanate with the functional groups of the Polymers with increased viscosity and crosslinking. The thickening and Depending on the type of surface-deactivated polyisocyanate, the reaction temperature is higher or lower below the softening temperature of the polymer.
Die Stabilität des unreagierten Systems, die Reaktionstemperatur und der Reaktionsverlauf werden bestimmt durch die Art des Polyisocyanats, durch Art und Menge des Oberflächenstabilisators, durch den Löslichkeitsparameter des funktionellen Polymers sowie durch Katalysatoren, Weichmacher und andere Hilfsmittel. Diese werden weitgehend in den eingangs erwähnten Schutzrechte beschrieben.The stability of the unreacted system, the reaction temperature and the course of the reaction are determined by the type of polyisocyanate, the type and amount of surface stabilizer, by the solubility parameter of the functional polymer and by catalysts, Plasticizers and other auxiliaries. These are largely in the beginning property rights mentioned.
Weiterhin sind der Applikation nachfolgende Bearbeitungsschritte des die Schicht oder das Pulver tragenden Substrates Gegenstand der Erfindung. Diese umfassen Schritte, wie sie z.B. bei der Bearbeitung des Substrates in seine endgültige Form durch Stanzen, Zuschneiden, Biegen, Falzen, Laminieren, etc.notwendig sind. Dabei wurde weiterhin unerwarteterweise festgestellt, dass der Film oder das Pulver in ihrem plastischen Zustand verarbeiten werden kann. Selbst nach Tagen oder Monaten kann die Schicht oder das Pulver auf Temperaturen oberhalb der Erweichungstemperatur des Polymern erhitzt werden, ohne dass Reaktion zwischen den funktionellen Gruppen des Polymern und den oberflächendesaktivierten Isocyanaten eintritt. Die Verarbeitung im plastischen Zustand kann dabei sogar unter mehrmaligem Erwärmen und Kühlen erfolgen.Furthermore, the application is followed by processing steps of the layer or the Powder-bearing substrate subject of the invention. These include steps as e.g. when processing the substrate into its final shape by punching, cutting, Bending, folding, laminating, etc. are necessary. This continued to happen unexpectedly found that the film or powder is in its plastic state can be processed. Even after days or months, the layer or powder can are heated to temperatures above the softening temperature of the polymer without that reaction between the functional groups of the polymer and the surface deactivated isocyanates occurs. Processing in the plastic state can take place even with repeated heating and cooling.
Die Filme oder Pulver sind vozugsweise lagerstabile, latent-reaktive Klebstoffsysteme.The films or powders are preferably storage-stable, latent-reactive Adhesive systems.
Als Polyisocyanate für das Verfahren sind alle Di- oder Polyisocyanate oder deren Gemische geeignet, sofern sie einen Schmelzpunkt oberhalb 40 °C aufweisen und sich durch bekannte Methoden in Pulverform mit Teilchengrösssen unter 200 µm überführen lassen. Es können aliphatische, cycloaliphatische, heterocyclische oder aromatische Polyisocyanate sein. Als Beispiele seien genannt: Diphenylmethan-4,4'-diisocyanat (MDI), Naphthalin-1,5-diisocyanat (NDI), 3,3'-Dimethyl-biphenyl-4,4'-diisocyanat (TODI), dimeres 1-Methyl-2,4-phenylen-diisocyanat (TDI-U), 3,3'-Diisocyanato-4,4'-dimethyl-N,N'diphenylharnstoff (TDIH), Additionsprodukt von 2 Mol 1-Methyl-2,4-phenylen-diisocyanat mit 1 Mol 1,2-Ethandiol, 1,4-Butandiol, 1,4-Cyclohexan-di-methanol, oder Ethanolamin, das Isocyanurat des IPDI (IPDI-T).All di- or polyisocyanates are suitable as polyisocyanates for the process or mixtures thereof, provided that they have a melting point above 40 ° C. and convert into powder form with particle sizes below 200 µm by known methods to let. It can be aliphatic, cycloaliphatic, heterocyclic or aromatic Be polyisocyanates. Examples include: diphenylmethane-4,4'-diisocyanate (MDI), Naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-biphenyl-4,4'-diisocyanate (TODI), dimeric 1-methyl-2,4-phenylene diisocyanate (TDI-U), 3,3'-diisocyanato-4,4'-dimethyl-N, N'diphenylurea (TDIH), addition product of 2 moles of 1-methyl-2,4-phenylene diisocyanate with 1 mol of 1,2-ethanediol, 1,4-butanediol, 1,4-cyclohexane-di-methanol, or ethanolamine, the Isocyanurate from IPDI (IPDI-T).
Die genannten Additionsprodukte zeigen nicht nur als wässrige Dispersionen die erfindungsgemässen Vorteile. Additionsprodukte aus 1-Methyl-2,4-phenylen-diisocyanat und 1,4 Butandiol oder 1,2 Ethandiol besitzten auch in festen und flüssigen lösungsmittelhaltigen oder lösungsmittelfreien Systemen sehr vorteilhafte Eigenschaften. Diese zeigen sich vor allem hinsichtlich ihrer niedrigen Aushärtungs- bzw. Vernetzungstemperatur, die im Temperaturbereich unter 90°C liegt. Damit ist die Verwendung dieser Mischung ob nun weitgehend auf Wasser- oder Polyolbasis sehr vorteilhaft für Beschichtungen und Verklebungen temperaturempfindlicher Substrate.The addition products mentioned show that not only as aqueous dispersions Advantages according to the invention. Addition products from 1-methyl-2,4-phenylene diisocyanate and 1,4 butanediol or 1,2 ethanediol are also available in solid and liquid solvents or solvent-free systems very advantageous properties. These show up all with regard to their low curing or crosslinking temperature, which in Temperature range is below 90 ° C. So the use of this mixture is now largely water or polyol based very beneficial for coatings and Bonding of temperature sensitive substrates.
Die Oberflächenstabilisierungsreaktion kann auf verschiedenen Wegen durchgeführt werden:
- Durch Dispersion des pulverförmigen Isocyanats in einer Lösung des Desaktivierungsmittels.
- Durch Eintragen einer Schmelze eines niederschmelzenden Polyisocyanats in eine Lösung des Desaktivierungsmittels in einem nichtlösenden flüssigen Dispersionsmittel.
- Durch Zugabe des Desaktivierungsmittels oder einer Lösung desselben, zur Dispersion der festen feinteiligen Isocyanate.
- By dispersing the powdered isocyanate in a solution of the deactivating agent.
- By introducing a melt of a low-melting polyisocyanate into a solution of the deactivating agent in a non-solvent liquid dispersing agent.
- By adding the deactivating agent or a solution thereof, to disperse the solid, finely divided isocyanates.
Die Konzentration des Desaktivierungsmittels soll 0.1 bis 25, bevorzugt 0.5 bis 8 Equivalentprozent betragen, bezogen auf die total vorhandenen Isocyanatgruppen.The concentration of the deactivating agent should be 0.1 to 25, preferably 0.5 to 8 equivalent percent amount, based on the total isocyanate groups present.
Oft muss für den erfindungsgemässen Einsatz die Teilchengrösse der pulverförmigen Polyisocyanate, durch eine der Synthese nachgeschaltete Feindispergierung oder Nassmahlung auf eine Teilchengrösse im Bereich von 0.5 bis 20 µ gebracht werden. Hierfür eignen sich Dissolver, Dispergiergeräte von Rotor-Stator Typ, Rührwerkskugelmühlen, Perlund Sandmühlen, Kugelmühlen und Reibspaltmühlen, bei Temperaturen unter 40 °C. Je nach Polyisocyanat und Verwendung erfolgt die Vermahlung am desaktivierten Polyisocyanat, in Gegenwart des Desaktivierungsmittels, im nichtreaktiven Dispergiermittel oder Wasser mit nachfolgender Desaktivierung. Das gemahlene und oberflächenstabilisierte Polyisocyanat lässt sich auch aus den Mahl-Dispersionen abtrennen und trocknen.For the use according to the invention, the particle size of the powdery powder must often be used Polyisocyanates, by a fine dispersion downstream of the synthesis or Wet grinding can be brought to a particle size in the range of 0.5 to 20 microns. Therefor dissolvers, rotor-stator type dispersers, agitator ball mills, Perlund are suitable Sand mills, ball mills and attrition mills, at temperatures below 40 ° C. Depending on Polyisocyanate and use is carried out on the deactivated polyisocyanate, in Presence of the deactivating agent in the non-reactive dispersant or water subsequent deactivation. The ground and surface stabilized polyisocyanate can also be separated from the grinding dispersions and dried.
Um die Oberflächendesaktivierung und die Vernetzungsreaktion zu steuern, können auch
Katalysatoren zugegeben werden. Bevorzugt sind solche Katalysatoren, welche in wässeriger
Lösung oder Dispersion hydrolysenstabil sind und später dann auch die wärmeaktivierte
Reaktion beschleunigen. Beispiele für Urethankatalysatoren sind organische Zinn-, Eisen-,
Blei-, Kobalt-, Wismuth-, Antimon-, Zink-Verbindungen oder ihre Mischungen.
Alkylmercaptidverbindungen des Dibutylzinns werden auf Grund der höheren
Hydrolysenstabilität bevorzugt.
Tertiäre Amine wie Dimethylbenzylamin, Diazabicyclo-undecen, sowie nichtflüchtige
Polyurethanschaumkatalysatoren auf tertiärer Aminbasis können für spezielle Zwecke oder in
Kombination mit Metallkatalysatoren verwendet werden, die katalanische Aktivität kann aber
durch Umsetzung mit dem Kohlendioxyd der Luft beeinträchtigt werden.To control the surface deactivation and the crosslinking reaction, catalysts can also be added. Preferred catalysts are those which are stable to hydrolysis in aqueous solution or dispersion and then later also accelerate the heat-activated reaction. Examples of urethane catalysts are organic tin, iron, lead, cobalt, bismuth, antimony, zinc compounds or their mixtures. Alkyl mercaptide compounds of dibutyltin are preferred due to their higher hydrolysis stability.
Tertiary amines such as dimethylbenzylamine, diazabicyclo-undecene, and non-volatile polyurethane foam catalysts based on tertiary amine can be used for special purposes or in combination with metal catalysts, but the Catalan activity can be impaired by reaction with the carbon dioxide in the air.
Die Konzentration der Katalysatoren liegt im Bereich von 0.001 bis 3 %, bevorzugt 0.01% - 1% bezogen auf das reaktive System.The concentration of the catalysts is in the range from 0.001 to 3%, preferably 0.01%. 1% based on the reactive system.
Als erfindungsgemässe Reaktionspartner der Polyisocyanate werden Polyurethane mit primären und sekundären Aminogruppen oder teilverseiftes Polyvinylacetat eingesetzt. As a reaction partner of the polyisocyanates according to the invention become polyurethanes with primary and secondary amino groups or partially saponified polyvinyl acetate used.
Diese Umsetzung erhöht die Reaktivität der funktionellen Gruppen des Polymeren gegenüber den Isocyanatgruppen, zu Lasten der Nebenreaktion mit Wasser.This reaction increases the reactivity of the functional groups of the polymer the isocyanate groups, at the expense of the side reaction with water.
Geeignet sind auch wasserlösliche hydroxyfunktionelle Bindemittel wie Polyvinylalkohol,
teilverseiftes Polyvinylacetat, Hydroxyethylcellulose, Hydroxypropylcellulose, sowie
wasserdispergierbare hydroxyfunktionelle Polyester, hydroxyfunktionelle Sulfopolyester, und
Polyurethandispersionen, Dispersionen von Polyamidoaminen, welche Carboxyl-, Hydroxylprimäre
oder sekundäre Aminogruppen tragen.
Ebenso können wässerige kolloidale Dispersionen oder kolloidale Lösungen mit
Teilchengrössen zwischen 1 - 100 nm in Kolloidmühlen hergestellt werden, ausgehend von
thermoplastischen Polymeren mit isocyanatreaktiven Gruppen. Beispiel sind höhermolekulare
feste Epoxyharze, Poly-ethylen-vinylalkohol und Poly-ethylen-co-acrylsäure.Also suitable are water-soluble hydroxyl-functional binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, hydroxyethyl cellulose, hydroxypropyl cellulose, and water-dispersible hydroxyl-functional polyesters, hydroxyl-functional sulfopolyesters, and polyurethane dispersions, dispersions of polyamidoamines which carry carboxyl, hydroxyl primary or secondary amino groups.
Likewise, aqueous colloidal dispersions or colloidal solutions with particle sizes between 1 - 100 nm can be produced in colloid mills, starting from thermoplastic polymers with isocyanate-reactive groups. Examples are high molecular weight solid epoxy resins, poly-ethylene-vinyl alcohol and poly-ethylene-co-acrylic acid.
Das Verhältnis zwischen den Isocyanatgruppen in den oberflächenstabilisierten feinteiligen Polyisocyanaten und der Summe der Hydroxyl- und Aminogruppen der Polymeren im weitgehend wasserfreiem und festem Zustand soll im Bereich 0.1 bis 1.5 betragen.The ratio between the isocyanate groups in the surface-stabilized fine particles Polyisocyanates and the sum of the hydroxyl and amino groups of the polymers in the largely anhydrous and solid state should be in the range 0.1 to 1.5.
In die resultierende hochviskose Paste oder niederviskose Mischung können weitere inerte oder funktionelle Zusätze eingemischt oder dispergiert werden. Zu den funktionellen Zusätzen gehören hydroxy- oder aminofunktionelle pulverförmige oder flüssige nieder- bis hochmolekulare Verbindungen, welche mit den festen Polyisocyanaten oberhalb der Reaktionstemperatur reagieren können. Die stöchiometrischen Verhältnisse sind entsprechend anzupassen. Als niedermolekulare Verbindungen werden Verbindungen mit Molekulargewichten zwischen 40 und 500 g/mol verstanden, unter hochmolekularen Verbindungen solche, deren Molekulargewichte zwischen 500 und 10000 g/mol liegen. Als Beispiele können angeführt werden: Niedermolekulare bis hochmolekulare flüssige Polyole oder/und Polyamine, feste polyfunktionelle Polyole oder/und aromatische Polyamine. Beispiele sind Triethanolamin, Butandiol, Trimethylolpropan, ethoxyliertes Bisphenol A, endständig ethoxylierte Polypropylenglykole, 3,5-Diethyl-toluylen-2,4- und 2-6-diamin, Poly-tetramethylenoxid-di-(p-aminobenzoat), Tris-hydroxyethyl-isocyanurat, Hydrochinonbis-hydroxyethylether, Pentaerythrit, 4,4'-Diamino-benzanilid, 4,4'-Methylen-bis-(2,6-diethylanilin).Further inert substances can be added to the resulting high-viscosity paste or low-viscosity mixture or functional additives can be mixed or dispersed. To the functional Additives include hydroxy or amino functional powdered or liquid low to high molecular compounds, which with the solid polyisocyanates above the Reaction temperature can react. The stoichiometric ratios are corresponding adapt. As low molecular weight compounds are compounds with Molecular weights between 40 and 500 g / mol understood by high molecular weight Compounds those whose molecular weights are between 500 and 10,000 g / mol. As Examples can be given: low molecular weight to high molecular weight liquid polyols or / and polyamines, solid polyfunctional polyols and / or aromatic polyamines. Examples are triethanolamine, butanediol, trimethylolpropane, ethoxylated bisphenol A, terminally ethoxylated polypropylene glycols, 3,5-diethyl-toluylene-2,4- and 2-6-diamine, Poly-tetramethylene oxide di (p-aminobenzoate), tris-hydroxyethyl isocyanurate, hydroquinone bis-hydroxyethyl ether, Pentaerythritol, 4,4'-diamino-benzanilide, 4,4'-methylene-bis- (2,6-diethylaniline).
Zu den inerten Zusätzen gehören beispielsweise Netzmittel, organische oder anorganische Verdickungsmittel, Weichmacher, Füllstoffe, Kunststoffpulver, Pigmente, Farbstoffe, Lichtstabilisatoren, Alterungsstabilisatoren, Korrosionsschutzmittel, Flammschutzmittel, Treibmittel, Haftharze, organofunktionelle Silane, kurzgeschnittene Fasern und gegebenenfalls geringe Mengen von inerten Lösungsmitteln.The inert additives include, for example, wetting agents, organic or inorganic Thickeners, plasticizers, fillers, plastic powders, pigments, dyes, Light stabilizers, aging stabilizers, corrosion inhibitors, flame retardants, Blowing agents, adhesive resins, organofunctional silanes, short cut fibers and optionally small amounts of inert solvents.
Die Vorteile der vorliegenden Erfindung liegen in der Trennung von Applikation der wässrigen Dispersion von der Vernetzungsreaktion d.h. der endgültigen Aushärtung. Damit können z.B. an einem Ort Klebstofffilme auf Holz, Glas oder anderweitige Substrate oder Unterlage aufgetragen werden, diese vorgefertigten Fabrikate gelagert und/oder verschickt werden und an einem anderen Ort zum Endprodukt ausgehärtet werden.The advantages of the present invention lie in the separation of application of the aqueous dispersion from the crosslinking reaction i.e. the final curing. In order to can e.g. in one place adhesive films on wood, glass or other substrates or Document are applied, these prefabricated products are stored and / or sent and be cured to the final product in another location.
Ein weiterer Vorteil des Verfahrens und der Verwendung der entsprechenden Produkte liegen in der Verwendung von Wasser als Dispersionsmedium Der Energieverbrauch zur Herstellung der Dispersionen ist gering. Der Anteil organischer Lösungsmittel minimal, was in einer aus Umweltschutzgesichtspunkten sehr vorteilhaften Verarbeitung resultiert.Another advantage of the method and the use of the corresponding Products lie in the use of water as the dispersion medium Energy consumption for the production of the dispersions is low. The proportion of organic Solvent minimal, which in a very environmental sense advantageous processing results.
Wenn von einer wässerigen Polymerdispersion ausgegangen wird, liegt ein weiterer Vorteil darin, dass auch oberflächendesaktivierte Polyisocyanate mit einem Schmelzpunkt im Bereich 40 bis 150 °C ohne Probleme eingearbeitet werden können. Die Vernetzungstemperaturen können im Bereich von 35 °C bis 90 °C liegen. Mit diesen niedrigen Vernetzungstemperaturen können auch temperaturempfindliche Substrate mit diesem Einkomponentensystem durch Wärmeeinwirkung verklebt werden.If an aqueous polymer dispersion is assumed, there is another advantage in that even surface deactivated polyisocyanates with a melting point in the range 40 to 150 ° C can be incorporated without problems. The cross-linking temperatures can range from 35 ° C to 90 ° C. With these low Cross-linking temperatures can also be used with temperature-sensitive substrates One-component system can be glued by heat.
Die aus der wässrigen Suspension, Dispersion oder Lösung erhaltene Schicht oder Pulver lässt sich monatelang lagern. Je nach den Lösungseigenschaften des festen Films für das Polyisocyanat ist die Lagerdauer bei Raumtemperatur oder leicht erhöhten Temperaturen jedoch unterschiedlich. Die Lagerdauer des erfindungsgemässen Systems im wasserfreien und unvernetzten Zustand ist wenigstens das 3-fache, üblicherweise mehr als das 10-fache der gleichen Mischung mit den gleichen Polyisocyanaten, welche nicht oberflächen-desaktiviert sind. Bei +2°C sind die erfindungsgemässen Schichten oder Pulver mindestens sechs Monate lagerstabil, bei Raumtemperatur jedoch mindestens 1 Monat lagerstabil und erfindungsgemäss verarbeitungsfähig. Der Begriff latent-reaktiv bezeichnet den Zustand der im wesentlichen wasserfreien Schicht oder Pulvers in der das oberflächendesaktivierte Polyisocyanat und das mit Isocyanaten reaktive Polymer im wesentlich unvernetzten Zustand vorliegen.The layer or powder obtained from the aqueous suspension, dispersion or solution can be stored for months. Depending on the solution properties of the solid film for the Polyisocyanate is the storage period at room temperature or slightly elevated temperatures however different. The storage period of the system according to the invention in anhydrous and uncrosslinked state is at least 3 times, usually more than 10 times same mixture with the same polyisocyanates, which is not surface-deactivated are. At + 2 ° C., the layers or powders according to the invention are at least six months stable in storage, but at least 1 month stable at room temperature and according to the invention processable. The term latent-reactive essentially describes the state of the anhydrous layer or powder in which the surface deactivated polyisocyanate and the polymer which is reactive with isocyanates is present in a substantially uncrosslinked state.
Die Wärmezufuhr für die thermoplastische Verarbeitung sowie die Vernetzung kann vorzugsweise mit Konvektions- oder Strahlungswärme erfolgen. Die lagerstabile wässerige Suspension, Dispersion oder Lösung aus oberflächendesaktivierten feinteiligen Polyisocyanaten und dispergierten oder wasserlöslichen Polymeren mit isocyanatreaktiven Gruppen kann auf die Oberfläche des zu verklebenden oder zu beschichtenden Substrates appliziert werden, insbesondere durch Pinseln, Sprühen, Spritzen, Rakeln, Spachteln, Giessen, Tauchen, Extrudieren oder durch Walzauftrag oder im Druckverfahren aufgetragen werden.The heat supply for thermoplastic processing and crosslinking can preferably with convection or radiant heat. The storage-stable watery Suspension, dispersion or solution of surface deactivated fine particles Polyisocyanates and dispersed or water-soluble polymers with isocyanate-reactive Groups can be on the surface of the substrate to be glued or coated are applied, in particular by brushing, spraying, spraying, knife coating, filling, Casting, dipping, extruding or applied by roller application or in the printing process become.
Im Falle der Verklebung von Substraten kann man wahlweise wie folgt vorgehen:
Die lagerstabile wässerige Dispersion von oberflächendesaktivierten feinteiligen Polyisocyanaten und dispergierten oder wasserlöslichen Polymeren mit isocyanatreaktiven Gruppen kann in die Form eines latent-reaktiven Klebefilms, Klebebandes, Klebevlieses oder -gewebes gebracht werden, der beidseitig Haftung aufbauen kann. Zur Herstellung von trägerfreien Formen, wie Filmen oder Bändern, wird die erfindungsgemässe Dispersion auf ein nichthaftendes Trägerband oder Trennpapier appliziert und das Wasser bei Raumtemperatur oder bei Temperaturen bis zur Erweichungstemperatur des Polymers verflüchtigt. Der Klebstoffilm kann nach Abkühlen vom Träger gelöst werden und bis zur Verwendung trägerfrei gelagert werden. Alternativ kann der Klebstoffilm mit dem Trägerpapier zusammen gelagert werden.The storage-stable aqueous dispersion of surface deactivated fine particle polyisocyanates and dispersed or Water-soluble polymers with isocyanate-reactive groups can take the form of a latent-reactive Adhesive film, adhesive tape, adhesive fleece or tissue are brought, the two-sided adhesion can build up. For the production of carrier-free forms, such as films or tapes, the dispersion according to the invention applied to a non-adhesive carrier tape or release paper and the water at room temperature or at temperatures up to the softening temperature of the polymer evaporates. After cooling, the adhesive film can be detached from the carrier and be stored carrier-free until use. Alternatively, the adhesive film can be used the backing paper are stored together.
Im Falle der Klebevliese oder -gewebe wird die reaktionsfähige Dispersion durch Sprühen, Spritzen, Rakeln, Giessen, Tauchen, Foulardieren, durch Walzauftrag oder im Druckverfahren appliziert, das Wasser bei Raumtemperatur oder bei Temperaturen bis zur Erweichungstemperatur des Polymers verflüchtigt, und das Klebevlies oder -gewebe, versehen oder imprägniert mit der latent wärmereaktiven Klebeschicht, bis zur Verwendung gelagert.In the case of adhesive nonwovens or woven fabrics, the reactive dispersion is sprayed, Spraying, knife coating, pouring, dipping, padding, by roller application or in Applied printing process, the water at room temperature or at temperatures up to Softening temperature of the polymer evaporates, and the adhesive fleece or fabric, provided or impregnated with the latently heat-reactive adhesive layer until use stored.
Die trägerfreien Klebefilme, Klebebänder, Klebevliese oder -gewebe dienen als Klebeschicht zwischen Substraten. Es ist auch möglich, Klebefilme, -vliese oder -gewebe einseitig auf eine Substratfläche im plastischen Zustand aufzubringen oder zu sintern. Dieses Laminat kann bis zur endgültigen Verklebung mit einer zweiten Substratoberfläche bei Raumtemperatur gelagert werden.The carrier-free adhesive films, tapes, adhesive fleeces or fabrics serve as an adhesive layer between substrates. It is also possible to apply adhesive films, fleeces or fabrics on one side Apply or sinter the substrate surface in the plastic state. This laminate can be up to for final gluing with a second substrate surface at room temperature be stored.
Die lagerstabile wässerige Dispersion von oberflächendesaktivierten feinteiligen Polyisocyanaten und dispergierten oder wasserlöslichen Polymeren mit isocyanatreaktiven Gruppen kann in die Form eines latentreaktiven Pulvers gebracht werden. Diese Pulver können als latentreaktive Klebestoffe oder zu Beschichtungszwecken, wie Pulverlacke, verwendet werden.The storage-stable aqueous dispersion of surface deactivated fine particle polyisocyanates and dispersed or Water-soluble polymers with isocyanate-reactive groups can take the form of a latent-reactive Powder are brought. These powders can be used as latent reactive adhesives or for coating purposes, like powder coatings.
Zur Herstellung von Pulvern aus den erfindungsgemässen Dispersionen können diese in einem Sprühturm versprüht werden. Die Temperatur der von unten eingeleiteten Luft soll unter der Erweichungstemperatur des Polymers und der Reaktionstemperatur des oberflächenblockierten Polyisocyanats bleiben.To produce powders from the dispersions according to the invention, these can be in be sprayed into a spray tower. The temperature of the air introduced from below should below the softening temperature of the polymer and the reaction temperature of the surface-blocked polyisocyanate remain.
Alternativ können die erfindungsgemässen Dispersionen auf die nicht haftende Oberfläche eines umlaufenden Bandes mit dehäsiven Oberflächen gesprüht oder mit einem Druckverfahren appliziert werden. Nach dem Verflüchtigen des Wassers werden die trockenen Partikel vom Band abgeschabt, gegebenenfalls gesiebt und klassiert, und bis zur Verwendung gelagert. Alternatively, the dispersions according to the invention can be applied to the non-stick surface of a circumferential tape sprayed with adhesive surfaces or with a Printing processes can be applied. After the water has evaporated, the dry particles scraped off the belt, sieved and classified if necessary, and up to Use stored.
Latent reaktive Pulver können auch aus trägerfreien Filmen oder Bändern durch Mahlprozesse, gegebenenfalls bei tiefen Temperaturen, hergestellt werden. Sie dienen als wärmereaktive vernetzbare Klebe- oder als Beschichtungspulver. Applikationsgeräte und -methoden sind Stand der Technik und dem Fachmann bekannt.Latent reactive powders can also be made from unsupported films or tapes Milling processes, possibly at low temperatures, are produced. They serve as heat-reactive crosslinkable adhesive or as a coating powder. Application devices and Methods are known in the art and known to the person skilled in the art.
Die mit dem Verfahren hergestellten latentreaktiven vorgefertigten Schichten dienen vorzugsweise als thermisch belastbare Klebeverbindung für flexible oder feste Substrate wie z.B. Metallen, Kunststoffen, Glas, Holz, Holzverbundstoffe, Karton, Folien, synthetischen Flächengebilden, Textilien,.The latent reactive prefabricated manufactured with the method Layers preferably serve as a thermally resilient adhesive connection for flexible or solid substrates such as Metals, plastics, glass, wood, wood composites, cardboard, Foils, synthetic fabrics, textiles ,.
Die so hergestellten reaktiven Beschichtungspulver lassen sich auch mit den Applikationsmethoden für Pulverlacke verarbeiten. Die Vemetzungstemperatur kann je nach Wahl des Polyisocyanats so niedrig sein, dass wärmeempfindliche Substrate, wie Kunststoffe, Textilien und Holz, ohne thermische Schädigung beschichtet werden können. Das Verfahren erlaubt auch die Beschichtungspulver auf dem Substrat nur zu sintern oder zu einer geschlossenen Schicht zu schmelzen. Die vollständige Vernetzung erfolgt dann bei einer späteren Wärmebehandlung, gegebenenfalls nach einem zusätzlichen mechanischen oder thermischen Bearbeitungschritt. The reactive coating powders thus produced can also be used with the Process application methods for powder coatings. The crosslinking temperature can vary Selection of the polyisocyanate should be so low that heat-sensitive substrates, such as plastics, Textiles and wood can be coated without thermal damage. The process also only allows the coating powders on the substrate to be sintered or sintered to melt a closed layer. The complete networking then takes place at one later heat treatment, possibly after an additional mechanical or thermal processing step.
- Lagerung AStorage A
- Dispersion bei Raumtemperatur applizieren, weitgehendes Entfernung des Wassers durch Verdunsten bei Raumtemperatur und/oder Eindsickern in die Unterlage, nach max. 3 Stunden Klebeflächen fügen, minimal 7 Tage bei Normalbedingungen lagern, dann 0.5 Std. auf 120 °C erhitzen (Objekttemperatur), wobei die Vemetzungsreaktion ausgelöst wird. Abkühlen und 24 Std. bei Normalbedingungen lagern.Apply dispersion at room temperature, extensive removal of the water by evaporation at room temperature and / or Infiltration into the underlay after max. Add 3 hours of adhesive surfaces, Store at least 7 days under normal conditions, then 0.5 hours at 120 ° C heat (object temperature), triggering the crosslinking reaction becomes. Cool and store for 24 hours under normal conditions.
- Lagerung BStorage B
- Wie Lagerung A, aber ohne Wärmebehandlung.Like storage A, but without heat treatment.
- Lagerung CStorage C
- Auf Klebefläche auftragen, weitgehendes Entfernung des Wassers durch Verdunsten bei Raumtemperatur und/oder Eindsickern in die Unterlage. Die mit Klebstoffschicht versehene Fläche offen an der Luft für mindestens 30 Tage liegen lassen. Klebeflächen fügen und unter Klammerdruck während 0.5 Std. auf 120 °C erhitzen, wobei die Vernetzungsreaktion ausgelöst wird. Abkühlen und 24 Std. bei Normalbedingungen lagern.Apply to the adhesive surface, removing most of the water Evaporation at room temperature and / or infiltration into the surface. The surface provided with adhesive layer is open to the air for Leave at least 30 days. Add adhesive surfaces and under Heat clamp pressure to 120 ° C for 0.5 hours, the Crosslinking reaction is triggered. Cool and 24 hours at Store normal conditions.
- Lagerung DStorage D
-
Flüssige Dispersion mit SDSI während 30 Tagen bei Raumtemperatur lagern,
dann auf Klebefläche applizieren. Weiter wie bei Lagerung A oder
C
- Abkürzung SDSI:
- Surface Deactivated Solid Isocyanate oder oberflächendesaktivierte festes Isocyanat
- Abbreviation SDSI:
- Surface Deactivated Solid Isocyanate
Prüfung der Temperaturbeständigkeit oder Wärmestandfestigkeit der Verklebungen: Prüflinge mit 100x20x5 mm3 aus Buchenholz resp. 25x100xd mm3 aus synthetischem Material wurden einfach überlappend press-verklebt, Ueberlappung 10 mm, Klebefläche 20x10 mm2. Um bei der Heissverklebung die Nebenreaktionen von Wasser mit Isocyanaten möglichst auszuschalten, wurden die Holzprüflinge in einem Umluftofen unter Vakuum (Restdruck 0.1bar) während 0.5 Stunden auf 120°C erhitzt.Testing the temperature resistance or heat resistance of the bonds: test specimens with 100x20x5 mm 3 made of beech wood resp. 25x100xd mm 3 made of synthetic material were simply overlapped press-glued, overlap 10 mm, adhesive surface 20x10 mm 2 . In order to eliminate the side reactions of water with isocyanates as much as possible when hot gluing, the wood specimens were heated in a forced air oven under vacuum (residual pressure 0.1 bar) at 120 ° C for 0.5 hours.
Für die Bestimmung der Temperaturfestigkeit nach Lagerungen A bis C wurden die Prüflinge senkrecht in den Umluftofen gehängt und mit 300 g belastet. Die Temperatur wurde alle 15The test specimens were used to determine the temperature resistance after storage A to C. hung vertically in the convection oven and loaded with 300 g. The temperature became every 15
Minuten um 10 °C erhöht. Haftverlust der Klebeflächen führte zum Fallen der Gewichte.Minutes increased by 10 ° C. Loss of adhesion of the adhesive surfaces led to the weights falling.
Obere Prüftemperatur begrenzt auf 150 °C.Upper test temperature limited to 150 ° C.
Bestimmung der Wasserbeständigkeit: Prüflinge im Wasser bei Normaltemperatur während 4 Tagen lagern. Qualitative Beurteilung der Festigkeit im nassen Zustand.Determination of water resistance: test specimens in water at normal temperature during 4 Days. Qualitative assessment of strength when wet.
Es bedeuten:
Abweichende oder andere Prüfbedingungen oder Prüfungen sind jeweils angegeben.Deviating or different test conditions or tests are indicated in each case.
Unter dem Dissolver wurde die folgende Suspensionen von oberflächendesaktivierten Polyisocyanaten
hergestellt:
Verwendete Klebstoffdispersionen:
Herstellung der Klebstoffdispersionen. Allgemeine Vorschrift:Production of the adhesive dispersions. General rule:
Es wurde mit dem Dissolver ein reaktiver Dispersionsklebstoff mit den angegebenen Polyisocvanaten
wie folgt hergestellt:
Die Klebstoffmischungen wurden mit einer Spiralrakel auf die Klebeflächen von Buchenholzprüflingen aufgebracht, dann gemäss den Lagerungen A - C behandelt, dann geprüft wie angegeben. Das Auftragsgewicht betrug nach der Trocknung etwa 100 g/m2. The adhesive mixtures were applied to the adhesive surfaces of beech wood specimens with a spiral doctor blade, then treated in accordance with the bearings A - C, then tested as indicated. The application weight after drying was about 100 g / m 2 .
Vernetzungsversuche mit Klebstoffen basierend auf KEM 2010 (neutralisiert) und
verschiedenen Suspensionen von Polyisocyanaten
30 Min. /120 °C
Wärmestandfestigkeit °C
nur Normalbedingungen Wärmestandfestigkeit °C
1 Monat offen, fügen, dann 30 Min./120 °C,
Wärmestandfestigkeit °C
1 Monat flüssig bei Normalbed. dann Lagerung A.
Wärmestandfestigkeit °C
30 min. / 120 ° C
Heat resistance ° C
only normal conditions heat resistance ° C
Open for 1 month, add, then 30 minutes / 120 ° C,
Heat resistance ° C
1 month liquid at normal conditions then storage A.
Heat resistance ° C
Vernetzungsversuche mit Klebstoffen basierend auf KEM 2010 (neutralisiert) und
verschiedenen Suspensionen von Polyisocyanaten
30 Min. / 120 °C Wärmestandfestigkeit °C
nur Normalbedingungen Wärmestandfestigkeit °C
1 Monat offen, fügen, dann 30 Min./120 °C, Wärmestandfestigkeit °C
1 Monat flüssig bei Normalbed. dann Lagerung A.
Wärmestandfestigkeit °C
30 min. / 120 ° C heat resistance ° C
only normal conditions heat resistance ° C
Open for 1 month, add, then 30 minutes / 120 ° C, heat resistance ° C
1 month liquid at normal conditions then storage A.
Heat resistance ° C
Vernetzungsversuche mit Klebstoffen basierend auf Polyurethandispersion Dispercoll U 54
und verschiedenen Suspensionen von Polyisocyanaten
30 Min. / 120 °C Wärmestandfestigkeit °C
nur Normalbedingungen Wärmestandfestigkeit °C
1 Monat offen, fügen, dann 30 Min./120 °C, Wärmestandfestigkeit °C
30 min. / 120 ° C heat resistance ° C
only normal conditions heat resistance ° C
Open for 1 month, add, then 30 minutes / 120 ° C, heat resistance ° C
Die Klebstoffdispersionen wurden mit Spiralrakel auf Spinnvliese aus Polyethylenterephtalat (Lutradur 7225, Flächengewicht 25 g/m2, Freudenberg KG, D-Weinheim) aufgetragen. Die Vliese wurden im frischem Zustand von der Unterlage getrennt und senkrecht hängend bei Normalbedingungen getrocknet.The adhesive dispersions were applied with a spiral doctor blade to spunbonded fabrics made of polyethylene terephthalate (Lutradur 7225, basis weight 25 g / m2, Freudenberg KG, D-Weinheim). The Nonwovens were separated from the base in the fresh state and hung vertically Normal conditions dried.
Nach 10 tägiger Lagerdauer wurden die trockenen Vliese zwischen zwei Buchenhölzern von
5 mm Dicke unter einem mechanischem Druck von 2 kp/cm2 während 30 Minuten auf 120 °C
erhitzt (Pressverklebung). Der Verbund wurde anschliessend während 24 Stunden drucklos
bei Normalbedingungen gelagert. Folgende Eigenschaften wurden an den Prüflingen
bestimmt:
Beispiel 22 wurde analog wiederholt, wobei auf Spinnvliese verzichtet wurde. Es entstand eine komplett trägerfreie, feste Klebeschicht, die bei Prüfung auf Wärmestandfestigkeit die zu Beispiel 22 analogen Werte zeigte.Example 22 was repeated analogously, spunbonded fabrics being dispensed with. It came into being a completely carrier-free, firm adhesive layer, which when tested for heat resistance the Example 22 showed analog values.
Auf Prüflinge mit den Dimensionen 100x25x3 mm3 wurde die reaktive Klebstoffdispersion
nach Beispiel 14 appliziert, Trockengewicht ca. 100 g/m2. Nach Verflüchtigung des Wassers
wurden die Prüflinge 3 Tage bei Normalbedingungen gelagert. Die beschichteten Flächen
wurden auf 80 °C (das heisst knapp über dem Erweichungspunkt des Polymers) erwärmt und
eine einfach überlappende Pressverklebung, Klebefläche 200 mm2, erzeugt. Sofort wurde die
Temperatur auf 120 °C erhöht und 30 Minuten gehalten.. Bei dieser Temperatur erfolgt die
Vernetzung. Anschliessend lagern während 24 Stunden bei Normalbedingungen.
Es wurden bestimmt:
Eine Klebstoffzusammensetzung wurde analog Beispiel 13 hergestellt und die wässrige Dispersion bei Raumtemperatur aufgetragen. Das Entfernen des Wassers erfolgte durch Verdunsten bei Raumtemperatur und/oder Eindringen in die Unterlage. Die feste Schicht wurde über einen Zeitraum von 5 Monaten bei +2°C offen liegen gelassen. Die Klebeflächen wurden danach zusammengefügt und unter Klammerdruck während 0.5 Std. auf 120°C erhitzt, wobei die Vernetzungsreaktion ausgelöst wurde. Abschliessend erfolgte eine 24 stündige Lagerung bei Raumtemperatur bei Raumtemperatur. Die Resultate hinsichtlich Wärmestandfestigkeit und Wasserlagerung entsprachen denen in Beispiel 13.An adhesive composition was prepared analogously to Example 13 and the aqueous one Dispersion applied at room temperature. The water was removed by Evaporation at room temperature and / or penetration into the mat. The solid layer was left open for a period of 5 months at + 2 ° C. The adhesive surfaces were then assembled and clamped at 120 ° C for 0.5 hours heated, whereby the crosslinking reaction was triggered. Finally there was a 24th hours storage at room temperature at room temperature. The results regarding Heat resistance and water storage corresponded to those in Example 13.
Herstellung, Applikation und Lagerung erfolgte analog Beispiel 26. Danach wurde das aus Unterlage und fester Klebstoffschicht bestehende Gesamtsystem dreimal auf 80°C über den Erweichungspunkt des Polymeren erwärmt und wieder abgekühlt. Anschliessend erfolgte das Aushärten durch halbstündiges Erwärmen auf 120°C. Die Resultate hinsichtlich Wärmestandfestigkeit und Wasserlagerung entsprachen denen in Beispiel 13.Production, application and storage were carried out analogously to Example 26. After that it was finished Underlay and solid adhesive layer existing system three times to 80 ° C above the Softening point of the polymer warmed and cooled again. Then it happened Cure by heating to 120 ° C for half an hour. The results regarding Heat resistance and water storage corresponded to those in Example 13.
Eine wässrige Dispersion, die der Zusammensetzung aus Beispiel 13 entspach, wurde mittels Sprühtrocknung in ein festes weitgehend wasserfreies Pulver überführt. Die Applikation, Lagerung und Vernetzung erfolgte analog Lagerung C. Die Resultate hinsichtlich Wärmestandfestigkeit und Wasserlagerung entsprachen denen in Beispiel 13.An aqueous dispersion which corresponded to the composition from Example 13 was removed using Spray drying converted into a solid, largely anhydrous powder. The application, Storage and crosslinking were carried out in the same way as storage C. Heat resistance and water storage corresponded to those in Example 13.
Claims (5)
- Aqueous dispersion containing at least one surface-deactivated solid fine-particle polyisocyanate and at least one isocyanate-reactive polymer, characterised in that the isocyanate-reactive polymer is selected from the group consisting of an aqueous dispersion of polyurethanes with primary and secondary amino groups or an aqueous dispersion of partially saponified polyvinyl acetate, which after drying of the dispersion below the reaction temperature of the surface-deactivated polyisocyanate allow the formation of a solid film.
- Aqueous dispersion according to claim 1, characterised in that the polyisocyanate displays a melting point in the range from 40°C to 150°C.
- Aqueous dispersion according to claim 1 or 2, characterised in that the polyisocyanate displays a particle size of 0.5 µm to 20 µm.
- Aqueous dispersion according to one of claims 1 to 3, characterised in that the polyisocyanate is selected from the group consisting of diphenyl methane-4,4'-diisocyanate (MDI), naphthaline-1,5-diisocyanate (NDI), 3,3'-dimethyl biphenyl-4,4'-diisocyanate (TODI), dimeric 1-methyl-2,4-phenylene diisocyanate (TDI-U), 3,3'-diisocyanato-4,4'-dimethyl-N,N'-diphenyl urea (TDIH), isocyanurate of isophorone diisocyanate (IPDI-T).
- Aqueous dispersion according to claim 4, characterised in that the polyisocyanate is diphenyl methane-4,4'-diisocyanate (MDI) with a particle size below 5 µm.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00109963A EP1029879B1 (en) | 1997-12-11 | 1997-12-11 | Aquous dispersion containing a surface-deactivated polyisocyanate |
PT00109963T PT1029879E (en) | 1997-12-11 | 1997-12-11 | AQUOSA DISPERSATION CONTAINING A SURFACIALLY DEACTIVATED POLYISOCYANATE |
DE59711521T DE59711521D1 (en) | 1997-12-11 | 1997-12-11 | Aqueous dispersion containing a surface deactivated polyisocyanate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00109963A EP1029879B1 (en) | 1997-12-11 | 1997-12-11 | Aquous dispersion containing a surface-deactivated polyisocyanate |
EP97810969A EP0922720B1 (en) | 1997-12-11 | 1997-12-11 | Preparation process and use of storage-stable latent reactive layers or powders from surface-deactivated solid polyisocyanates and dispersion polymers showing functional groups |
Related Parent Applications (2)
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EP97810969.2 Division | 1997-12-11 | ||
EP97810969A Division EP0922720B1 (en) | 1997-12-11 | 1997-12-11 | Preparation process and use of storage-stable latent reactive layers or powders from surface-deactivated solid polyisocyanates and dispersion polymers showing functional groups |
Publications (2)
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EP1029879A1 EP1029879A1 (en) | 2000-08-23 |
EP1029879B1 true EP1029879B1 (en) | 2004-04-14 |
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ID=8230516
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EP97810969A Expired - Lifetime EP0922720B1 (en) | 1997-12-11 | 1997-12-11 | Preparation process and use of storage-stable latent reactive layers or powders from surface-deactivated solid polyisocyanates and dispersion polymers showing functional groups |
EP00109963A Expired - Lifetime EP1029879B1 (en) | 1997-12-11 | 1997-12-11 | Aquous dispersion containing a surface-deactivated polyisocyanate |
EP98956754A Expired - Lifetime EP1037935B1 (en) | 1997-12-11 | 1998-12-09 | Method for producing and using storage-stable, latent-reactive layers or powders of surface-deactivated, solid polyisocyanates and dispersion polymers with functional groups |
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EP97810969A Expired - Lifetime EP0922720B1 (en) | 1997-12-11 | 1997-12-11 | Preparation process and use of storage-stable latent reactive layers or powders from surface-deactivated solid polyisocyanates and dispersion polymers showing functional groups |
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Country Status (17)
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US (2) | US6348548B1 (en) |
EP (3) | EP0922720B1 (en) |
JP (1) | JP4099312B2 (en) |
KR (1) | KR100603781B1 (en) |
CN (1) | CN1137178C (en) |
AT (3) | ATE203035T1 (en) |
AU (1) | AU748817B2 (en) |
BR (1) | BR9813562A (en) |
CA (1) | CA2314320A1 (en) |
DE (2) | DE59705314D1 (en) |
DK (3) | DK0922720T3 (en) |
ES (3) | ES2161429T3 (en) |
GR (1) | GR3036520T3 (en) |
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DE19924138A1 (en) | 1999-05-26 | 2000-11-30 | Henkel Kgaa | Detachable adhesive connections |
DE19951599A1 (en) | 1999-10-27 | 2001-05-23 | Henkel Kgaa | Process for adhesive separation of adhesive bonds |
TWI279408B (en) | 2000-01-31 | 2007-04-21 | Vantico Ag | Epoxy resin composition |
DE10012826A1 (en) * | 2000-03-16 | 2001-09-20 | Bayer Ag | Adhesive preparations |
DE10020160A1 (en) * | 2000-04-25 | 2001-10-31 | Bayer Ag | Adhesive preparations |
EP1164154A1 (en) * | 2000-06-15 | 2001-12-19 | Ag Bayer | Pressure-sensitive adhesives with improved shearing resistance at higher temperatures |
DE10034637B4 (en) | 2000-07-15 | 2004-04-08 | Jowat Ag | Storage stable isocyanate dispersions |
DE10037884A1 (en) | 2000-08-03 | 2002-02-21 | Henkel Kgaa | Accelerated curing process |
DE10106630A1 (en) | 2001-02-12 | 2002-08-22 | Jowat Lobers U Frank Gmbh & Co | Self-supporting reactive hot melt adhesive element and its use |
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